Inorganic-organo titanate polymeric film

ABSTRACT

ORIENTED OPAQUE ULTRATHIN FILMS COMPRISING THERMOPLASTIC POLYMERS CONTAINING UP TO ABOUT 60 PARTS BY WEIGHT OF AN INORGANIC FILLER-ORGANO TITANATE COMPOUND ARE DESCRIBED. THE FILMS ARE PREPARED BY EXTRUDING THE COMPOSITIONS AS FILMS AND THEREAFTER DRAWING THE RESULTANT FILMS AT A TEMPERATURE BELOW THAT AT WHICH THE FILMS REMAIN TRANSLUCENT. THE FILMS OR OUR INVENTION ARE USEFUL AS PACKAGING MATERIAL IN PREPARING ULTRATHIN PAPER, AND IN LAMINATES, NON-WOVEN FABRIC, RUG BACKING AND MESH STRUCTURES.

v United States Patent Ofice 3,697,475 Patented Oct. 10, 1972 3,697,475INORGANIC-ORGANO TITANATE POLYMERIC FILM Horton H. Morris and Paul I.Prescott, Macon, Ga., as-

signors to Freeport Sulphur Company, New York,

No brawiug. Filed Oct. 30, 1969, Ser. No. 872,757 Int. Cl. C08f 45/06;C08k 1/12 US. Cl. 260-41 A 7 Claims ABSTRACT OF THE DISCLOSURE Orientedopaque ultrathin films comprising thermoplastic polymers containing upto about '60 parts by weight of an inorganic filler-organo titanatecompound are described. The films are prepared by extruding thecompositions as films and thereafter drawing the resultant films at atemperature below that at which the films remain translucent. The filmsof our invention are useful as packaging material in preparing ultrathinpaper, and in laminates, non-woven fabric, rug backing and meshstructures.

BACKGROUND OF THE INVENTION (a) Field of invention This inventionrelates to thin oriented films of thermoplastic polymers. Moreparticularly, the invention relates to thermoplastic polymers which havebeen modified by the incorporation therein of an inorganic filler, thesurface of which has been reacted with an organic derivative of orthotitanic acid containing at least two hydrolyzable groups, and which havebeen oriented under conditions which produce a white, opaque film ofhigh brightness and tensile strength.

(b) Description of the prior art Paper has been made conventionally byfelting naturally occurring cellulosic fibers such as cotton and wood.To produce cellulosic paper of publication grade, it is frequently thepractice to fill the body stock, i.e., the raw uncoated paper from thefelting and subsequent drying and smoothing operations, with an inert,white mineral filler and to coat both sides of the body stock with ahigh brightness white pigment, e.g., kaolin clays, in a binder of caseinlatex, starch or other adhesives to achieve a sheet opacity of at least88 to 90% and a TAPPI brightness of 70%. The resulting publication gradepaper stock has a weight of 34 to 45 pounds per ream, a thickness of 3to 4 mils, uncalendered, and a tensile strength of 3000 to 5000 p.s.i.for uncoated stock.

OBJECTS OF THE INVENTION One object of this invention is to producethermoplastic films suitable as a replacement for paper having highopacity, brightness and tensile strength and low weight.

A further object of this invention is to provide thermoplastic filmssuitable as a replacement for paper which contain from about 2 to about60 percent of a treated inorganic filler in a thermoplastic material.

Still another object is to provide colored thermoplastic films suitableas a replacement for paper.

Yet another object of the invention is to provide fibrillated filledfilms.

SUMMARY OF THE INVENTION These and other objects are attained byincorporating into a thermoplastic material an inorganic filler whichhas been reacted with an organic derivative of ortho titanic acidcontaining at least two hydrolyzable groups, forming films therefrom andcold drawing the films under conditions which produce a white, opaquefilm of high brightness and tensile strength. To obtain colored films,inorganic pigments conventionally used as coloring agents, which havebeen reacted with an organo titanium compound containing at least twohydrolyzable groups are used or may be included with other organotitanium treated inorganic fillers. Alternatively, organic dyes may beincorporated in the organo titanium compound which is reacted with thefiller.

The organo titanium compounds used to react with the inorganic fillermaterial are represented by the formula Ti(OR) R wherein R is a hydrogenradical containing from 1 to 12 carbon atoms and R may be OCOR", OR" ora hydrocarbon substituted silicic acid radical (OSiR") wherein R" is asubstituted or unsubstituted hydrocarbon radical having from 1 to 40carbon atoms and wherein R'" is a substituted or unsubstitutedhydrocarbon radical having from 6 to 40 carbon atoms providing that R'and R are not identical. In the formula m is equal to 2 or 3. At leasttwo hydrolyzable groups, preferably OR groupings, must be present in theorgano titanium compound in order that hydrolysis of the organo titaniumcompound occurs followed by its polymerization to produce a film oforgano-substituted titanium oxide at the filler surface. Through thisreaction the filler is provided with a hydrophobic, organophilic film.

The organo titanium compounds can be prepared by reacting 1 mol ofTi(OR) with from 1 to 2 mols of a compound represented by the formula ARwherein A is hydrogen or a group capable of reacting to remove an ORfrom the Ti(O'R) molecule and R is as described above. A mixture of twoor more compounds of the formula AR may be used. The preparation ofillustrative organo titanium compounds is more particularly described inLangkammerers US. Pat. 2,621,193 [see also page 15 of the E. I. du Pontde Nemours & Co. publication entitled Tyzor, Versatile Chemicals forIndustry (1965, revised 1966) which describes the reaction product ofLangkammerers process as a monomer whose formula is identical to theTi(OR) R' formula given above, but which also points out that themonomers are unstable and under certain conditions may decompose byreacting with one another to yield a polymeric reaction product of astructure identical to that shown in col. 4, lines 51-58 of theLangkammerer patent; as pointed out by Langkammerer (col. 4, lines40-42), the exact structure of this polymeric reaction product isunknown].

Reverting to the starting material Ti(OR) R may be selected from thegroup consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkarylradicals containing from 1 to 12 carbon atoms. Specific examples ofcompounds represented by the formulae are tetramethyl titanate,tetraethyl titanate (ethyl orthotitanate), tetrabutyl, tetraisopropyl,tetraamyl, tetraoctyl, tetradodecyl, tetra-Z-ethylhexyl, etrabenzyl,tetraphenyl and tetra-betanaphthyl titanates.

The radical R" mentioned above represents a hydrocarbon radical havingfrom 1 to 40 carbon atoms taken from the group consisting of alkyl,cycloalkyl, aryl, aralkyl, alkaryl hydrocarbon radicals which maycontain various substituents such as halogens, e.g., a perfluoro methylradical, hydroxyl groups, keto group (radical of levulinic acid) amino,nitro and heterocyclic groups. Examples of R" groups are methyl, ethyl,propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, octadecyl,cyclohexyl, cycloheptyl, phenyl, naphthyl, tolyl, xylyl, benzyl, phenylethyl, chlorophenyl, dibromophenyl, 2,3-dihydroxy propoxy. The varioushydrocarbon radicals may contain aliphatic unsaturation as well asaromatic unsaturation. Perfluoro compounds may be used. R' is of similarscope but with exclusion of radicals containing. or less carbon atoms.

A preferred class of compounds represented by the formula AR are theorganic aromatic and aliphatic carboxylic acids. The resulting organotitanium compound may be called an ester carboxylate or an esteranhydride of ortho titanic acid. Among the aliphatic and aromaticorganic acids that may be used are straight or branch chain, saturatedor unsaturated, substituted or unsubstituted monoor poly-carboxylicacids including such acids as stearic, palmitic, ricinoleic, linoleic,lauric, myristic, oleic, benzoic, caproic, caprylic, nonylic, capric,linseed oil acids, castor oil acids, tall oil acids, cocoanut oil acids,soybean oil acids, tung oil acids, perfiuorooctanoic acid, phthalicacid, adipic acid, etc.

A second class of useful compounds which generally will be used inconjunction with one of the acids cited above, although they can be usedas sole component of the reaction with the Ti(OR) are the organicalcohols or organic phenols. Among such compounds are 2-phenoxyethanol,m-cresol, diethylene glycol, 2,6-dioctadecylcresol,1-(2-pyridylazo)-2-naphthol, naphthol, anisyl alcohol, glycerol,geraniol, etc.

In some cases the combined effect of the two classes just cited may beobtained by using an ester such as the triglyceride of ricinoleic acid.

The inorganic fillers of this invention comprise fillers in particulate(of any particle size distribution and any particle shape) or fibrousform. As long as the inorganic filler contains at its surface reactivehydroxy groups and/ or about,0.1 to about 2 weight percent based on thefiller of adsorbed water, the specific chemical nature of the filler isnot important. Suitable inorganic fillers include clay, calciumcarbonate, barium sulfate, glass in the form of fibers or thinplatelets, vermiculite, asbestos, mica, etc. If a colored product isdesired any of the well-known inorganic coloring pigments may be usedincluding iron oxides, Prussian blue, zinc chromate, cobalt blue,ultramarine blue, etc. All of these materials generally have theproperty of being chemically inert to the polymeric materials and arerelatively heat resistant as compared to the polymeric material.

Clays are a preferred inorganic filler because of the superiorproperties of the treated clay of our invention in comparison with theuntreated clay, the ready availability of clays and their relatively lowcost. Illustrative clays are untreated or treated (e.g., calcined ordelaminated) English or Georgia filler and coating clays. Clays arecomposed of two atomic lattice structural units. One

consists of two sheets of closely packed oxygen atoms or hydroxyl groupsin which aluminum (and occasionally iron or magnesium) atoms areembedded in octahedral coordination. The second unit is built of silicatetrahedrons, being arranged so as to form a hexagonal network, which isrepeatedindefinitely to form a sheet-like structure. In kaolinite, thestructure is composed of a single tetrahedral sheet and a singlealuminum octahedral sheet combined in a unit so that the tips of thesilica tetrahedrons and one of the layers of the octahedral sheet form acommon layer. The aluminum sheet, in a unit cell, carries six hydroxylgroups, which appear on one surface of the cell and two hydroxyl groupswhich project toward the center of the cell. The structural formula canbe represented by (OI-I) Si Al O Clay minerals therefore containhydroxyl groups which can be pictured as potential reaction sites. Clayminerals are alsovery finely divided and have surface areas varying fromabout one square meter per gram up into the 100 square meter per gramrange. Like all finely divided and fibrous materials water is generallyadsorbed onto the clay particles in very small amounts and can serve asa reaction site.

The inorganic filler-organo titanate products are formed by dissolvingthe organo titanate in an anhydrous organic solvent,.wetting the surfaceof the inorganic filler with the solution and maintaining contactbetween the two materials until reaction is completed. Generally thereaction occurs spontaneously but, in some cases, gentle heating isrequired to speed the reaction. The solvent and hydrolysis products arethen removed by distillation or filtration. As a result of thistreatment it is believed an extremely thin layer of an organicsubstituted titanium compound or hydrated titanium oxide is formed byhydrolysis of the titanium compound on the surface of the inorganicmaterial, due to the presence of hydroxyl groups in the inorganicfiller, e.g., in conventional clays, or due to the presence of a traceof adsorbed water. Whatever the mechanism the product is stable tofurther processing conditions.

The amount of organo titanate, Ti(OR) R used will vary from about 0.5 toabout 6 weight percent based on the dry weight of the inorganicmaterial, the amount used being partially dependent on the surface areaof the inorganic material since it is essential that substantially allof the surface area be reacted. The organo titanate should be dissolvedin a solvent which does not react with the titanate. Such solvents arehydrocarbons such as naphtha, hexane, octanes, etc. and chlorinatedhydrocarbons such as trichloroethylene. The solvents should beanhydrous. In the event that the organotitanium compound is volatile theinorganic material may be directly reacted with it by passing thegaseous material across the inorganic surfaces. The volatile organotitanate may be diluted with a dry inert gas to facilitate this process.If the inorganic material lacks reactive hydroxyl groups at its surfaceand has been subjected to severe drying conditions, it will be necessaryto mix it with water, such that its surface contains from about 0.1 toabout 2 weight percent of water prior to the reaction with the organotitanate.

The particle size and shape of the inorganic material is important onlywith respect to the end use of the filled polymeric composition. Thus, avery fine particle size may be desired when the polymer composition isdrawn to produce films of 0.5 mil thickness.

The inorganic filler-organo titanate products used in the invention areset out and claimed in the commonly assigned application of Horton H.Morris and J. P. Oliver, viz., 'Ser. No. 872,370, filed Oct. 30, 1969.

The thermoplastic polymers of our invention cover a variety of types.Any thermoplastic polymer can be used, the term thermoplastic as used inour application applies to synthetic resins that may be softened byheat, and then regain their original properties upon cooling. It is notintended that the polymer be void of any crosslinking. For example,impact polystyrenes which contain crosslinked rubber can be used.

' An important class of polymers are those obtained by polymerizing orcopolymerizing organic compounds containing a carbon-carbon double bond.Such polymers include the polyalkenes formed from monomers such asethylene, propylene, butylene and isobutylene; the polydialkenes formedfrom monomers such as butadiene and isoprene; the halogenatedpolyalkenes from monomers such as dichlorodifiuoroethylene, brominatedethylenes, tetrachloroethylene, chlorotrifluoroethylene, andtetrafluoroethylene; the vinyl resins such as polyvinyl acetal,polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinylformal, polyvinyl carbazone, polyvinyl chloride and polyvinylidenechloride; the polystyrenes formed from such monomers as butadiene,substituted butadienes as isoprene, styrene, alpha-methyl styrene andthe chlorostyrenes; and acrylic resins formed from such monomers asacrylic acid, methacrylic acid and the esters and nitriles thereof suchas methyl acrylate, ethyl acrylate, methyl-methacrylate, acrylonitrileand methacrylonitrile. Another related group of resins include thecopolymers and terpolymers of the preceding monomers. Examples arecopolymerized butadiene-styrene, vinyl chloride-vinyl acetate, vinylchloride-vinyloxyethanol and ethylenemaleic anhydride.

An additional class of thermoplastic polymers are condensation polymerssuch as the nylons and polyurethanes.

Preferred polymers are those synthetic polymers of monoethylenicallyunsaturated monomers containing two to six carbon atoms and especiallythose polymers and copolymers of ethylene or propylene and othermonoethylenically unsaturated monomers. Polymeric compositions useful inthis invention are included among the polymeric compositions disclosedin the commonly assigned application of Horton H. Morris, J. P. Oliverand P. I. Prescott, viz., Ser. No. 872,752, filed Oct. 30, 1969.

The compositions of this invention are prepared by simply mixing thepolymeric material with the treated filler using any of the conventionalmeans common to the plastics industry. Thus, the polymer may be mixed onroll mills at elevated temperatures until soft and the dried filleradded during the milling action. Alternatively, the polymer and fillermay be mixed together in ball mills, dough mixers with or without addedsolvent and other conventional additives such as plasticizers,antioxidants, lubricants, dyes, etc. Thereafter, the compositions areextruded in conventional apparatus at elevated temperatures to formfilms having any desired thickness. These films then may be reduced inthickness in two steps, the first occurring immediately after the filmemerges from the extruder before it is quenched on the chill rolls andthe second occurring after the film has cooled substantially below 100C. In the first reduction in thickness of the film, the film remainstranslucent. In the second step, the thickness of the film is furtherreduced and becomes white and opaque. For example, in the firstreduction the film thickness can be reduced to 1.5 to mils while in thesecond step, the film can be further reduced to 0.5 to 1.5 mils.However, the opaque films of our invention may have a thickness of asmuch as 5 mils. The opacity of our films is due to the production of amultitude of tiny voids produced during the cold drawing step. Suchfilms are in contrast to the compositions disclosed in the commonlyassigned application of Morris, Oliver and Prescott referred to above.In that application, any films produced from the compositions havecomparatively few voids in comparison to the films of our invention.

The second step, which can be termed the orienting operation (althoughorientation does occur in the first reduction), may be performed onconventional apparatus or by hand. Alternatively, the compositions maybe merely conventionally drawn and oriented at a conventionaltemperature, for the first drawing step, to directly produce atranslucent drawn film, followed by drawing said film at a temperaturebelow that temperature at which the film remains translucent to producean opaque film of about 0.5 to about 1.5 mil thickness.

The temperature of the drawing steps willdepend on the particularpolymer being used. The first drawing step is carried out attemperatures that produce a translucent material. The second step may becarried out at tempera tures from room temperature, i.e., 20-30 C. up tothe temperature at which opacity fails to appear. In general thetemperature for the second step should not be above 100 C. although somepolymer compositions might be drawn at slightly higher temperatures andstill yield an opaque product.

The films of this invention can have a 7 to 16 pound weight per ream permil of thickness, or can be made as low as 7 to 8 pounds per ream. Theyhave been prepared in thicknesses ranging from 0.5 to 1.5 mi-lsdepending on the thickness of the undrawn film and on the temperature atwhich the film is drawn. The brightness of the films is at least-70*%and can be improved to about 97% as measured on an automatic colorbrightness tester (Martin Sweets Company). The films have a tensilestrength of 25,000 to 27,000 p.s.i. which is far above that ofconventional cellulosic paper. They are thus stronger, thinner and lowerin weight than cellulosic paper, whiter than conventional publicationpaper and even in the 0.5 mil thickness can have the same opacity. Thefilms have a glossy surface.

The films of the invention which can be called ultrathin paper areparticularly valuable as publication paper since their low weight willreduce postal rates and their thinner sheets will reduce bulk. The filmsare also useful in other applications where high strength, opacity andthinness are desirable such as in top liners for paperboard, breadwrappers, plastic bags for packaging or garbage disposal and otherwrapping, covering or containing uses. They may also be furthermodified, as by surface oxidation, to improve their receptivity.

The films of the invention may also be used in capacitors. A perennialproblem with capacitors is the degradation of the chlorinated organicdielectric fluid. The degradation products are the cause of prematurecapacitor failure which may be prevented or at least delayed by using aplastic film containing filler active sites on which will serve toscavenge the degradation products. The organo substituted titanatetreated clays in the ultrathin paper will remove impurities and thepaper because of its open surface structure will tend to promotemigration of the dielectric fluid.

The films of the invention can also be machine fibrillated to produce anopen net-like structure. The edges of the fibrillated film have tinyfibrils which act to hold a chopped staple, made from the fibrillatedfilm, when made into a non-woven sheet. The fibriliated film may be usedin laminates, non-woven fabric, rug backing and other applications wherethe mesh structure is filled, coated or impregnated.

The following examples are given in illustration and are not intended aslimitations on the scope of this invention. All parts and percentagesare by Weight unless otherwise stated.

Example I (a) Triisopropyl monooleic titanate was prepared by mixing 258grams (0.91 mole) of tetraisopropyl titanate with 256 grams (0.91 mole)of oleic acid at room temperature accompanied by stirring. The mixturebecame warm immediately indicating the occurrence of the desiredreaction, and was allowed to stand for several minutes. The product wastriisopropyl monooleyl titanate dissolved in isopropyl alcohol. Withoutremoving the alcohol the product was mixed with 50 pounds of naphtha toproduce a low viscosity solution containing the titanate. Thereafterthirty pounds of a fine particle size delaminated kaolin was addedslowly to the naphtha solution accompanied by vigorous stirring toprevent lumping of the clay. After complete addition of the clay to givea. 38% solids dispersion in naphtha, the mixture was stirred for anadditional half hour. The dispersion was then dried to remove naphthaand isopropyl alcohol and the product therefrom was pulverized. Theproduct did not appear, on visual examination, to 'be any different fromthe original kaolin.

To determine the eflect of the treatment of the clay with the organotitanium derivative 3 grams of the OX-l and 3 grams of the untreatedkaolin were separately shaken vigorously with 15 grams of water in atest tube. The tubes were then allowed to stand until the kaolin eithersettled to the bottom or floated on the surface of the water. The amountof OX-l which settled out, as determined gravimetrically, was less than0.1 percent showing that OX-1 was hydrophobic whereas all of theuntreated kaolin was wetted by the water within 10 seconds of thestanding period. When the OX-l was added to an organic solvent such astoluene, it dispersed therein readily and completely in contrast to theuntreated clay which balls or gums up in toluene.

(b) Three hundred and fifty grams of polypropylene having a melt indexof 15 grams per 10 minutes at 230 C. were bonded on a rubber millbetween rolls heated to 360 F. and mixed thereon for about 15 minutes.One hundred and fifty grams of OX-l were then slowly added and millingwas continued for another 15 minutes. The composition thus formed wasremoved from the rubber mill, cooled and granulated. The composition didnot stick to the hot rolls and was easily removed therefrom. To insurecomplete dispersion of the OX-l in the polypropylene the composition waspelletized by passing it through an extruder equipped with one 40 meshand one 250 mesh screen at a temperature of 260 C. into a cold waterquench bath using a die which produced a A; inch rod. The cooled rod wasthen pelletized and dried in a vacuum oven at 100 C. The pelletswerethen extruded through a slit die adjusted to produce a mil film. Thefeed zone and the metering zone on the screw were heated to 245 C. andthe die was maintained at 238 C. The film was extruded at a constantrate onto a cold quench roll revolving at a controlled circumferentialspeed. By changing the circumferential speed from 7 to 11 and then to 16feet per minute films were produced having thicknesses of 3, 2 and 1 milrespectively. The films thus produced contained 30 weight percent oftreated clay, and were slightly yellow and translucent.

The l, 2 and 3 mil films were oriented at a temperature of about 23 C.to produce white opaque thin sheets, having the properties shown inTable I as compared to the properties of the undrawn film.

TABLE I Undrawn Drawn Mon. nrnmnnf fi Brightness, TAPPI, percent 29. 698. 7-97. 7 Opacity, percent 44. 4 89. 7 Dominant wavelength, mu. 574. 6Color purity, percent 4. 05 Visual elfieieney, percent. 91. 2Brightness, percent 86 Tensile strength, p.s.i 25, 000

Using the same technique shown in Example I(b) and the samepolypropylene, 3 mil films were prepared containing 10, 20 and ,30weight percent OX-1. The films were then machine drawn at a 9X ratio atan oven temperature which was set at 135 C. to give white opaque films.(The oven was 10 feet long and the film was drawn after it had gone onlyone foot into the oven. The entry speed of the film into the oven wasabout 20 feet per minute. The exit speed of the oriented film was 190feet. per minute.) Part of the composition containing 30% OX-l wasfibrillated as it was drawn and had a net-like structure. Scanningelectron microphotographs show that the cut edges of the fibrillatedfilm contain discrete fibrils.

Example III Two compositions were made .froma polyproplene having a meltindex of 6.5 grams per ten minutes at 230 C., one containing20 and theother 30 weight percent of. OX-l. The'compositions were extruded, asshown in Example I(b) for production of translucent films, to obtain a 5mil, slightly yellow and translucent film. When this film was hand drawnat room temperature ca. 20 30 C., it became white and opaque and had atensile strength of 25,000-27,000 psi Example IV To obtain coloredultrathin paper three dilferent inorganic pigments were reacted with thereaction product of tetraisopropyl titanate and oleic'acid in the samemanner as the clay was reacted in Example I(a). Thirty :grams of eachtreated pigment were added to a polypropylene having a melt index'of 4.0grams per 10 minutes at 230 C. on mill rolls andthen 70 grams of OX-1were added. The compositions thus produced were extruded into thin filmsand the resultant films cold drawn at about 23 C. to yield coloredopaque 1.5 mil film. The first pigment used was a synthetic iron oxideknownas Mapico Yellow Lemon of Columbia Carbon Company. The filmprepared using this. pigment was yellow-orange in color. When a zincchromate known as C.P. Zinc Yellow Imeprial Color and Chemical (HerculesPowder Co.) was used the final film was a bright pastel yellow and whena basic lead chromate deposited on a silica core known as Oncor M50 ofthe National Lead Co. was used the final film was a light pinkishorange.

Example V Four hundred grams of polyethylene having a melt index of 2grams per minute at 125 C. were bonded on a rubber mill between rollsheated to C. and mixed thereon for about 10 minutes. One hundred gramsof OX-1 were slowly added and milling was continued for another 15minutes. The composition thus formed was removed from the rubber mill,cooled and granulated. The granulated composition was pressed betweenplatens heated to C. to produce a 6 mil thick film. The film wastranslucent as pressed. However, when the film was drawn, by hand, atroom temperature (23 C.) it became white, opaque and 2.5 mil thick.

It is obvious that many variations may be made in this invention withoutdeparting from the spirit and scope thereof as defined in the appendedclaims.

What is claimed is:

1. An opaque and glossy film having an open surface structure comprisinga thermoplastic polymer having incorporated therein an inorganic fillerthe surfaces of which, prior to the incorporation step, have beenreacted with an organo titanium compound containing at least twohydrolyzable groups and which is represented by the formula Ti(OR) R'wherein R is a hydrocarbon radical containng from 1 to 12 carbon atomsand R isOC-OR", OR', or OSiR wherein R" -is a substituted orunsubstituted hydrocarbon radical having from 1 to 40 carbon atoms andwherein R' is a substituted or unsubstituted hydrocarbon radical havingfrom 6 to 40 carbon atoms providing that R'" and R are not identical andwherein m is equal to 2 or 3, and wherein said inorganic filler prior toreaction with said organo titanium compound contains at its surfaceeither adsorbed water, in an amount ranging from about 0.1 to about 2percent, weight percent, based on the filler, or reactive hydroxylgroups or both reactive hydroxyl groups and said adsorbed water, wherebythe hydroxylzable groups of said compound are hydrolyzed by saidadsorbed water or reactive hydroxyl groups, or both, to produce apolymeric organo titanium compound at the surfaces of said inorganicfiller.

2. An opaque film as in claim 1 wherein the thermoplastic polymer is apolymer of propylene.

3. An opaque film as in claim 1 wherein the organo titanium compound isthe equimolar reaction product of tetraisopropyl titanate and oleicacid.

4. An opaque film as in claim 1 wherein the thermo plastic polymer is apolymer of ethylene.

5. An opaque film as in claim 1 wherein the thermoplastic polymer ispolypropylene, and the organo titanium compound is triisopropylmonooleyl titanate.

6. A fibrillated opaque and glossy film having an open surface structurecomprising a thermoplastic polymer having incorporated therein aninorganic filler the surfaces of which, prior to the incorporation step,have been reacted with an organo titanium compound containing at leasttwo hydrolyzable groups and which is represented by the formula Ti(OR)R' wherein R is a hydrocarbon radical containing from 1 to 12 carbonatoms and R is OCOR", OR, or OSiR wherein R is a substituted orunsubstituted hydrocarbon radical having from 1 to 40 carbon atoms andwherein R is a substituted or unsubstituted hydrocarbon radical havingfrom 6 to 40 carbon atoms providing that R' and R are not identical andwherein m is equal to 2 or 3, and wherein said inorganic filler prior toreaction with said organo titanium compound contains at its surfaceeither adsorbed water, in an amount ranging from about 0.1 to about 2percent, weight percent, based on the filler, or reactive hydroxylgroups or both reactive hydroxyl groups and said adsorbed water, wherebythe hydrolyzable groups of said compound are hydrolyzed by said adsorbedwater or reactive hydroxy groups, or

10 both, to produce a polymeric oragno-titanium compound at the surfaceof said inorganic filler.

7. An opaque film as in claim 1 wherein the inorganic filler is clay.

References Cited UNITED STATES PATENTS LEWIS T. JACOBS, Primary ExaminerJ. H. 'DERRINGTON, Assistant Examiner US. Cl. X.R.

106-288 Q, 299, 308 Q; 260-37 N, 41 R, 41.5 R,

UNITED STATES Pl'lTENT OFFICE IEHTHREOAJIE CORRECTION Patent No. 3, 9Dated October 10, 97

' Invenrofls) H. H. Morris, et a1 It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

col." 2, lihelle, "hydrogen" should. be -"hydrocarbon 2, line 53,"formulae" should be formula --5 2, line 56 "etrabenzyl" should befetr'abenzyl LL, line 4.2, "Oliver" should 'be Olivier a, line 43,"872,370" should be 872,730

5, line 11, "Oliver" should be Olivier 5, line LLO, "Oliver" should beOlivier 6', line '29, "fibril-iated" should be fi'brillated 6, line-75,"bonded" should be banded line 17, "Imeprial" should be Imperial lines59-60, (Claim 1), "hydroxylzable" should be hydrolyz'able' 10, line 1(Claim 6), "Qragno" should be organo Signed and sealed this lst day ofMay 1973.

(SEAL) Attest:

EDWARD M. FLETCHER, JR. ROBERT GOTT'SCHALK Attesting OfficerCommissioner of Patents PORN PO 1050 (10- 9)

